MSI工艺制备C/SiC复合材料的氧化动力学和机理

以针刺整体炭毡为预制体, 采用CVD+MSI工艺制备了C/SiC复合材料, 借助XRD和SEM研究材料的微观组织, 通过等温氧化失重和非等温热重分析研究材料的氧化反应动力学和反应机理. 结果表明: MSI工艺所制备的C/SiC材料致密度高, 物相组成为类石墨结构的C、反应生成的SiC和残留Si. 其等温氧化反应机理: 第Ⅰ阶段为反应控制, 第Ⅱ和Ⅲ阶段为扩散和反应共同控制; 材料的非等温氧化过程呈现自催化特征, 氧化机理为随机成核, 氧化动力学参数为: lgA=8.752min^-1, E_a=169.167kJ·mol^-1. 与C/C材料相比, C/SiC材料有较差的低温氧化性能和稳定的高温氧化性能, 这与MSI的工艺特征密切相关.     

熔盐法在碳纤维表面制备抗氧化SiC涂层

采用熔盐法,以NaCl-KCl作熔盐介质,利用Si粉与碳纤维反应在纤维表面制备出均匀的SiC涂层。研究了反应温度、热处理时间和Si/C比对SiC涂层结构和形貌的影响。研究结果表明:随着热处理温度、热处理时间以及Si/C比的增加,纤维表面涂层厚度与SiC晶粒尺寸增加,但是涂层厚度增加随着Si/C比的增加变化较小。与未涂层碳纤维相比,SiC涂层明显改善了碳纤维的抗氧化性能。1350℃热处理3h制备的SiC涂层致密均匀,其起始氧化温度由540℃增加至650℃。     

SiC/PyC复合涂层碳纤维微观结构及氧化行为研究

采用两步法在碳纤维表面制备了碳化硅/热解碳(SiC/PyC)复合涂层,PyC内涂层的制备采用等温化学气相渗透法,SiC外涂层的制备采用碳热还原法.借助X射线衍射、场发射扫描电镜、透射电镜分析了SiC/PyC复合涂层碳纤维的物相组成以及微观结构,利用热重分析研究了SiC/PyC复合涂层、PyC涂层以及无涂层碳纤维的氧化行为.结果表明,在碳纤维表面制备的SiC/PyC复合涂层连续致密、厚度均匀,PyC内涂层厚度约为200nm,SiC外涂层厚度约为160nm,SiC层中存在大量孪晶面高度有序的SiC孪晶.SiC/PyC复合涂层能够有效地改善碳纤维的抗氧化性能,较无涂层碳纤维起始氧化温度提高了近250℃.     

SiO2涂层制备工艺对三维碳纤维编织体抗氧化性能的影响

采用溶胶-浸渍法,在三维碳纤维编织体的纤维表面涂覆SiO₂涂层。实验研究了涂层制备工艺对编织体抗氧化性能的影响。结果表明,纤维经丙酮、硝酸处理后,再采用粘度为0.01～0.012(Pa·s)、分子生长模式为线性的溶胶浸渍,当涂层厚度为0.5μm左右时,浸渍试样抗氧化性能好,完全氧化失重温度为900℃,较之原始编织体提高300℃。涂层过厚或过薄,编织体抗氧化性能下降,这是由于涂层在纤维表面分布不均匀或与纤维表面结合性较差引起的。     

2D-C/C复合材料氧化动力学模型及其氧化机理

用热重法研究了二维炭/炭(2D-C/C)复合材料的等温氧化, 提出了氧化动力学模型, 用SEM观察了样品不同氧化程度的微观形貌, 并探讨了材料的等温氧化机理。氧化分2个阶段: 线性氧化阶段, 氧化失重率小于约65%, 氧化速率处于稳定状态; 非线性氧化阶段, 氧化失重率约大于65%, 氧化速率急剧减小。Arrhenius曲线由折点在800~850℃之间的2条直线组成。线性氧化阶段, 活化能分别为217.2kJ/mol和157.0kJ/mol; 非线性氧化阶段, 反应级数分别为0.55和0.65, 活化能分别为219.3kJ/mol和182.0kJ/mol。通过实验验证, 氧化动力学模型可以较好地预测材料的恒温氧化。氧化从炭纤维与基体炭的界面开始, 基体氧化快于纤维, 氧化后期主要是纤维的氧化。在750~800℃, 氧化为化学反应控制; 在850~905℃, 氧化由化学反应和气体扩散共同控制, 但非线性氧化阶段气体扩散对氧化的贡献小于线性氧化阶段。      

C/SiC复合材料表面Si-C-B自愈合涂层的制备与抗氧化行为

采用化学气相沉积法(CVD)制备单质B和BCx分别对SiC涂层进行改性,在二维碳纤维增强碳化硅(2D C/sic)复合材料表面制备SiC/B/SiC和SiC/BCx/SiC两种多层白愈合涂层,并利用扫描电镜对多层涂层表面和断面进行显微分析. 700°C静态空气条件下氧化结果表明: CVD-B和CVD-BCx改性层氧化后生成的B2O3玻璃相可以较好地封填涂层微裂纹,氧化动力学受氧通过微裂纹和B2O3玻璃层的扩散共同控制;SiC/BCx/SiC-C/SiC复合材料氧化过程中氧化失重率更小,氧化10h后的强度保持率更高.     

SiO2涂层制备工艺对三维碳纤维编织体抗氧化性能的影响

采用溶胶-浸渍法,在三维碳纤维编织体的纤维表面涂覆SiO2涂层.实验研究了涂层制备工艺对编织体抗氧化性能的影响.结果表明,纤维经丙酮、硝酸处理后,再采用粘度为0.01～0.012(Pa@s)、分子生长模式为线性的溶胶浸渍,当涂层厚度为0.5μm左右时,浸渍试样抗氧化性能好,完全氧化失重温度为900℃,较之原始编织体提高300℃.涂层过厚或过薄,编织体抗氧化性能下降,这是由于涂层在纤维表面分布不均匀或与纤维表面结合性较差引起的.     

不同氧化温度下涂覆BN涂层SiC纤维的微观结构及性能研究

通过化学气相渗透(CVI)工艺在典型国产SiC纤维表面沉积BN涂层，并在800～1200℃的氧化环境下处理1 h。对涂覆BN涂层的SiC纤维氧化后的形貌、结构以及成分进行表征，通过单丝拉伸强度评价涂覆BN涂层的SiC纤维氧化后的性能变化。结果表明，氧化温度低于1000℃时，BN涂层及其氧化物层能够有效阻止O₂对内部SiC纤维的侵蚀，高于此温度时，SiC纤维被氧化。随着氧化温度的升高，涂覆BN涂层的SiC纤维表面氧化物经历α-B₂O₃→SiC_xO_y→非晶SiO₂的历程。涂覆BN涂层的SiC纤维单丝拉伸强度随着温度的升高呈衰减趋势，且BN涂层直接暴露在氧化环境下反而降低SiC纤维的抗氧化能力。纤维断裂的失效源先由BN涂层缺陷过渡为B₂O₃氧化层缺陷最终演变为SiO₂氧化层气孔缺陷。     

C-Si 梯度涂层对碳纤维性能的影响

本文提出并探索了在碳纤维表面化学气相沉积 C-Si 梯度涂层的新方法,研究了 C-Si 梯度涂层对碳纤维性能的影响。实验结果表明,碳纤维表面化学气相沉积 C-Si 梯度涂层结构中的 C,Si 元素均呈非晶态结构;梯度涂层能大幅度提高碳纤维的抗氧化性。梯度涂层减少了涂层与纤维基体的各种不匹配因素,缓和了涂层中热应力,限制了氧化反应的进行,使梯度涂层纤维氧化前后强度均明显高于 Si,SiC,SiO_2等单一涂层纤维。     

SiC纤维增强钛基复合材料界面反应机理

本文应用相图和扩散通道理论分析了SiC/Ti复合材料界面反应的过程及界面区微观形貌,SiC纤维的表面状态直接影响着SiC/Ti界面反应的扩散通道。在SiC纤维表面涂覆TiC,或涂覆碳基涂层使Ti₃SiC₂层优先形成,能有效地控制界面反应,保护SiC纤维,界面区中反应产物层的排列顺序不一定与扩散通道所示的相顺序一一对应。      

Effect of Temperature on the Synthesis of SiC Coating on Carbon Fibers by the Reaction of SiO with the Deposited Pyrolytic Carbon Layer

The influence of reaction temperature on the preparation of SiC coating on carbon fibers by the reaction of silicon monoxide with the deposited pyrolytic carbon (PyC) layer has been discussed. With rising reaction temperature, the thickness of SiC layer increases and the SiC grain is coarsening. The apparent activation energy for the synthesis of SiC layer is about 103.3 kJ/mol. The oxidation resistance of carbon fiber can be improved by the SiC/PyC layers significantly. The initial oxidation temperature of the SiC/PyC coated carbon fiber is about 300°C higher than that of the uncoated carbon fiber. The oxidation of the SiC/PyC coated carbon fiber is owing to the diffusion of oxygen through the cracks generated by the mismatch of thermal expansion.     

Si-Al-Ir Oxidation Resistant Coating for Carbon/Carbon Composites by Slurry Dipping

A Si-Al-Ir oxidation resistant coating was prepared for SiC coated carbon/carbon composites by slurry dipping. The phase composition, microstructure and oxidation resistance of the as-prepared Si-Al-Ir coating were studied by XRD (X-ray diffraction), SEM (scanning electron microscopy), and isothermal oxidation test at 1773 K in air, respectively. The surface of the as-prepared Si-Al-Ir coating was dense and the thickness was approximately 100 μm. Its anti-oxidation property was superior to that of the inner...     

MoSi2-SiC 抗氧化涂层对碳/碳复合材料弯曲性能的影响

在C/C 复合材料表面制备了MoSi₂-SiC 抗氧化涂层, 分析了涂层工艺对C/C 复合材料组织的影响, 测试了材料的室温弯曲力学性能。结果表明, 该工艺在C/C 复合材料表面生成抗氧化涂层的同时, 基材内部的层间和纤维束界面, 以及孔隙周围也被硅化。C/C 复合材料经涂层工艺处理后, 弯曲断裂行为发生改变, 弯曲强度明显升高,塑性有一定程度的降低。      

Verification and prediction of residual strength of C/SiC composites under non-stress oxidation

This article describes the strength behavior of C/SiC composites under non-stress oxidation. The oxidation kinetics model of a ceramic matrix composite contains both a reaction-controlled process and a diffusion-controlled process. The oxidation process has an effect on the fiber volume fraction, radius, and the composite interface shear stress. We obtained the residual strength of unidirectional C/SiC composites under 400–900 °C oxidation with non-stress environments by combining the mass loss rate model with the strength failure model at room temperature. This model considers the different components of the system to be subject to oxidation at different temperature ranges. Then, the influence of oxidation temperature, oxidation time, and fiber volume fraction on residual strength was studied. Experiments on C/SiC composites at 650 and 800 °C in an air environment with non-stress conditions were then performed, and the theoretical results of C/SiC composites were in good agreement with the experimental data.     

The anti-oxidation behavior and infrared emissivity property of SiC/ZrSiO4–SiO2 coating

In order to improve the oxidation resistance and decrease the infrared emissivity of carbon/carbon(C/C) composites, the SiC and SiC/ZrSiO₄–SiO₂ (SZS) coating were prepared by pack cementation and slurry painting method. The phase compositions and microstructures of the as-prepared coatings were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive spectrometer. The anti-oxidation property, failure and infrared emissivity of single SiC coating and SZS coating were investigated. The results show that the weight loss of single SiC coated sample reached 2.1 ± 0.025 % after 58 h isothermal oxidation at 1,500 °C. While the SZS coating exhibits superior oxidation resistance and can protect C/C matrix from oxidation for more than 198 h with a weight-gain of 3.67 ± 0.025 %. The failure mechanisms of single SiC coating are mainly resulting from unself-healing defects caused by the CO₂ gas which generated during the oxidation process of SiC. The investigation of infrared emissivity property reveals that, the infrared emissivity of SZS coating increases gradually from 0.45 to 0.72 between 3 and 14 μm. The infrared emissivity at 500 °C increases gradually from 0.2 to 0.65 between 3 and 14 μm. The coupled effect between dipole moments and lattice vibration in higher temperature becomes weaker, which in turn lead to the reducing of infrared emissivity in turn. From the anti-oxidation and infrared emissivity property point of view, the SZS coating may be one of the most promising candidates for the anti-oxidation at high temperature and low infrared emissivity of C/C composite.     

W-Mo-Si/SiC Oxidation Protective Coating for Carbon/Carbon Composites

A W-Mo-Si/SiC double-layer oxidation protective coating for carbon/carbon （C/C） composites was prepared by a two-step pack cementation technique. XRD （X-ray diffraction） and SEM （scanning electron microscopy）results show that the coating obtained by the first step pack cementation was a thin inner buffer layer of SiC with some cracks and pores, and a new phase of （WxMo1-x）Si2 appeared after the second step pack cementation. Oxidation test shows that, after oxidation in air at 1773 K for 175 h and thermal cycling between 1773 K and room temperature for 18 times, the weight loss of the W-Mo-Si/SiC coated C/C composites was only 2.06%. The oxidation protective failure of the W-Mo-Si/SiC coating was attributed to the formation of some penetrable cracks in the coating.     

Oxidation behavior and mechanical properties of C/SiC composites with Si-MoSi2 oxidation protection coating

A new kind of oxidation protection coating of Si-MoSi₂ was developed for three dimensional carbon fiber reinforced silicon carbide composites which could be serviced upto 1550 °C. The overall oxidation behavior could be divided into three stages: (i) 500 °C < T < 800 °C, the oxidation mechanism was considered to be controlled by the chemical reaction between carbon and oxygen; (ii) 800 °C < T < 1100 °C, the oxidation of the composite was controlled by the diffusion of oxygen through the micro-cracks, and; (iii) T > 1100 °C, the oxidation of SiC became significant and was controlled by oxygen diffusion through the SiC layer. Microstructural analysis revealed that the oxidation protection coating had a three-layer structure: the out layer is oxidation layer of silica glass, the media layer is Si + MoSi₂ layer, and the inside layer is SiC layer. The coated C/SiC composites exhibited excellent oxidation resistance and thermal shock resistance. After the composites annealed at 1550 °C for 50 h in air and 1550 °C 100 °C thermal shock for 50 times, the flexural strength was maintained by 85% and 80% respectively. The relationship between oxidation weight change and flexural strength revealed the criteria for protection coating was that the maximum point of oxidation weight gain was the failure starting point for oxidation protection coating.     

Preparation of SiC Fiber Reinforced Nickel Matrix Composite

A method of preparing continuous(Al+Al2O3)-coated SiC fiber reinforced nickel matrix composite was presented,in which the diffusion between SiC fiber and nickel matrix could be prevented.Magnetron sputtering is used to deposit Ni coating on the surface of the(Al+Al2O3)-coated SiC fiber in preparation of the precursor wires.It is shown that the deposited Ni coating combines well with the(Al+Al2O3) coating and has little negative effect on the tensile strength of(Al+Al2O3)-coated SiC fiber.Solid-state diffusion bonding process is employed to prepare the(Al+Al2O3)-coated SiC fiber reinforced nickel matrix with 37% fibers in volume.The solid-state diffusion bonding process is optimized and the optimum parameters are temperature of 870,pressure of 50 MPa and holding time of 2 h.Under this condition,the precursor wires can diffuse well,composite of full density can be formed and the(Al+Al2O3) coating is effective to restrict the reaction between SiC fiber and nickel matrix.